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It sounds like your default workspace has ended up with a snapshot (a saved set of windows that you want to return to in the future) saved into it. That would supercede your general preference setting for what page you want new windows to point at.

The way to test this theory would be to start the browser up, then open the "Workspaces" window. If the selected item in the list on the left of the window that appears has a small camera icon associated with it, you've got a snapshot. What you'll want to do is either delete that workspace, or set up the browser window(s) as you'd like them to appear when you start up the browser and take a new snapshot with the camera button at the bottom of the window.

Does that help?